Modified polymeric polyhydric alcohols



Patented Feb. 12, 1946 irs'o stares parser MODH HED POLYMERHU PQLYHYDRHC ALCQIPZQHJS I No Drawing. Application November 12, was, Serial No. 510.63%

1% Claims. (Cl. Wit-87) This invention relates to polymeric organic compounds and more particularly to the modification oi! polymeric polyhydric alcohols.

Polymeric polyhydric alcohols such as cellulose,

polyvinyl alcohol and the like have attained great utility in the arts because of their useful properties. These polymeric polyhydric alcohols sufier. however, from certain disadvantages, particularly with respect to sensitivit towards. water and insufficient solubility in organic solvents.

This invention has as an object the provision of new modified polymers. A further object is the improvement of polymeric polyhydric alcohols. Other objects will appear hereinafter.

These objects are accomplished by the following invention of new modified polymeric polyhydric alcohols and their preparation by the reaction of polymeric polyhydric alcohols in the presence of an aqueous solution of an alkaline catalyst with a 2,5-dihydrothiophene-1-dioxide inert to metallic sodium at room temperature, i. e. approximately 25 C.

In general, the modification is effected by heating the polymeric polyhydric alcohol with 2,5- dihydrothiophene-l-dioxide in the presence of an alkaline catalyst. In a preferred modification of the invention, a mixture of 2,5-dihydrothiophene-l-dioxide with a polymeric alcohol in a weight ratio, such that for each equivalent weight of hydroxyl group in the polymeric material there is present preferably at least one mole of 2,5-dihydrothiophene-l--dioxide, is heated with stirring in a vessel at 65-'75 C., preferably'under an inert oxygen-free atmosphere. After the contents are thoroughly mixed, about 4% (based on the weight of 2,5-dihydrothiophene-l-dioxide) of sodium or potassium hydroxide dissolved in an equal weight of water is added with vigorous stirring. The reaction is exemplified below for the polyvinyl alcohol reaction. -oH,-cH-cHTcHcrn-oi1- a Hc=on n on on H c H -oH,-H om-orr CHr-CH- l i 1 HC--CH: HCCH: H ----CH: mo cm H3O CH: HIC Hi s s s .0 O1 0! The reaction may be generalized as follows: i (on).+rnr i==on (H0)..-. P o-oH- cH H CH, H: CH:

In this P is the nonhydroxyl residue of the polyvigorous meric polyhydric alcohol, at the number of hydroxyls in the molecule thereof and at the number of thiophene dioxide molecules entering into reaction with the polymeric polyhydric alcohol.

In the case of polymeric polyhydric alcohols which are initially water soluble, e. g., polyvinyl alcohol, the products usuall become progressively less water soluble as the reaction proceeds. The reaction, therefore, can be followed easily by testing the water solubility of samples removed from the reaction vessel. In most cases the reaction is relatively rapid, and usually not more than /2 hour's heating is required to impart water insolubility.

Corresponding ethers of water-insoluble polymeric alcohols (e. g., cellulose) maybe prepared by the following procedure: The polymer, shredded and steeped in aqueous alkali, is filtered or pressed as dry as possible and then added with stirring to 2,5-dihydrothiophene-ldioxide heated to -75 C. The reaction is usually much slower than with water-soluble polymers and generally heating must be continued for a longer period to bring about a substantial degree of reaction.

Although 2,5-dihydrothiophene-l-dioxide 'itself reacts with water in the presence of alkali, the reaction with a polymeric polyhydric alcohol may, nevertheless, be carried out in aqueous solution providing the thiophene-dioxide is added in several portions. For example, the polymer may be dissolved or dispersed in a minimum amount of water containing 1-10% of alkali (based on the polymer) and then heated to 65- C. with stirring under a substantially oxygenfree atmosphere while the 2,5-dihydrothiophenel-dioxide is added in several portions.

The more detailed practice of the invention is illustrated by the following examples wherein parts given are by weight. There are, of course, many forms of the invention other than these specific embodiments.

Example I This example illustrates the preparation of a 1,1-dioxotetrahydrothienyl-3 ether of polyvinyl alcohol in the absence of a solvent.

One-half part of potassium hydroxide is dissolved in one part of water in a reaction vessel equipped with stirrer and nitrogen inlet. 'Iio this is added parts of 2,5-dihydrothiophene-1-dioxide (prepared from butadiene and sulfur dioxide as described in German Patent 506,839) and the mixture is stirred and heated at 65-'I0 C. When the 2,5-dihydrothiophene-1-dioxide has all melted and the air in the vessel has been displaced with nitrogen, 13.5 parts oi! medium viscosity polyvinyl alcohol (any commercial grade is satisfactory) is added with stirring. The vessel is heated at 65-70 C. and stirred for 24 hours. Two hundred parts of water is then added. The water-insoluble, brown, taffy-like material is washed by kneading in water until most of the color is removed. It may be purified further by dissolving in aqueous formic acid or aqueous dioxane and pouring the solution so obtained into a large volume of water with vigorous stirring. The light amber-colored product is soft, plastic, somewhat tacky and rather elastic, It dries to a hard, horny solid which contains 14.38% of sulfur. solutions of this ether in dioxane/water (90/10) and the solid ether can be molded into strong, rigid bars.

- Example II This. example illustrates the preparation of a 1,l-dioxotetrahydrothienyl-3 ether of a waterinsoluble polymeric alcohol (cellulose).

Fifty-four parts of cotton linters is pulped in 2,000 parts of 18% sodium hydroxide and allowed 7 to stand one hour. alkali and pressed to a press ratio of 4:1. This alkali cellulose is then added to 1760 parts of 2,5-dihydrothiophene-l-dioxide heated to 65-'l0 C. in a nitrogen-filled vessel equipped with a stirrer. After the mixture has been heated and stirred for 15 hours, 4,000 parts of water is added and the contents stirred for A hour. The modifled cellulose iscollected by flltratlonand washed several times by slurrying inwater until the washings are no longer alkaline and then dried. The product contains 8.7% of sulfur, softens at 280 C. and can be pressed into strong, tough, translucent sheets at 250 C. and 8,000 lbs/sq. in.

Example III Clear, hard films can be cast from the v It is then drained of excess Example V This example illustrates the preparation, in aqueous solution, of a 1,1-dioxotetrahydrothienyl-3 ether of a water-soluble polymeric alcohol.

Thirteen hundred and fifty parts of medium viscosity polyvinyl alcohol is\ dissolved in 1250 parts of water-containing 20 parts of potassium hydroxide and heated to 75 C. Eleven hundred andeighty parts of 2,5-dihydrothiophene-l-dioxide is added in several portions with stirring over the course of three hours. ture isthen raised to 100 C. for two hours, after which the mixture is cooled and. acetone run in until the polymer is precipitated. The polymer is washed by kneading in acetone and then dried.

'It is insoluble in water but soluble in aqueous acetone and contains 9% of sulfur. By, using larger proportions of 2,5-dihydrothiophene-ldioxide, the amount of sulfur contained in the higher sulfur content are substantially insoluble in water.

Films of the water-soluble ethers can be cast directly from the reaction mixture. water is then evaporated, there is obtained a film,

, which is much less water sensitive than films of polyvinyl alcohol, more elastic and more rubbery. The present invention is generic to the reaction, in the presence of an alkaline alkali metal catalyst, of any polymeric polyhydric alcohol with dioxide, and 20 parts of 50% aqueous potassium hydroxide solution. The product isolated as described in Example I, is an almost white powder, softening at 125-130" C. as compared to 155-160 C. for the original copolymer. It contains 6.4% of sulfur.

- Example IV This example illustrates the reaction of woodpulp with 2,5-dihydrothiophene-l-dioxide.

Fifty-four parts of wood pulp is added to 1300 parts of 2,5-dihydrothiophene-l-dioxide; heated at -'l0 C. and stirred vigorously until well dispersed. The air in the vessel is displaced with nitrogen and 75'parts of 50% aqueous potassium hydroxide is then added. The mixture is heated at 65-70 C. and stirred for 18 hours, after which the flask is cooled, 2,000 parts of water. is added and the insoluble modified cellulose collected by filtration, washed by slurrying repeatedly in water until free of alkali, and flnallydried. The product weighs 69 parts, softens at 280 C.,and contains 7.6% of sulfur. At a temperature of 250 C. it can be molded into tough, translucent sheets.

and 2,5-dihydrothiophene-1 dioxide inert to metallic sodium at 25 C. including 2,5-dihydrothiophene-l-dioxide, 3-methyl-2,5-dihydrothiophene 1 dioxide, 2 methyl 2,5 dihydrothiophene-L,

nitrate, cellulose acetate, cellulose propionate,

cellulose glycolate; cellulose ethers such as ethyl cellulose, benzyl cellulose; at least partially hydrolyzed'vinyl ester polymers, including copolymers, such as polymers of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl chloride with vinyl acetate, vinyl acetate withethylene, vinyl acetate with vinyl thioacetate; starch. 7

Any alkaline alkali metal catalyst may be employed including alkali metal hydroxides and alkoxides including sodium hydroxide. potassium hydroxide, sodium ethoxide or methoxide and potassium ethoxide or methoxide. Quaternary ammonium compounds may also be employed. Sodium hydroxide and potassium hydroxide are preferred catalysts. a

The mixing of the reactants and the catalyst The tempera- When the.

or the introduction of them into the reaction vessel may be, accomplished by any convenient means.

The nature of the'products depends to some extent upon the ratio of the reactants,

decomposition temperature of this reactant. In

the presence of a solvent, however, the lower temperature limit does not depend upon the melting point of this thiophene derivative and the reaction can be carried out even at room temperature. However, since longer periods are required at the lower temperature, it is preferred in this case also to operatejust below the decomposition temperature of the thiophene derivative. In the case of 2,5-dihydrothiophene-ldioxide, for example, the preferred temperature range is 65-75 C.

The modified polymeric polyhydric alcohol products are ethers of the polymeric polyhydric alcohol with a, 3-hydroxythiolane-l-dioxide. By the generic name thiolane is meant a saturated heterocyclic structure of five members, of which one is a sulfur atom and the other four carbon atoms. The ethers are of 3-hydroxythiolanes which 3-hydroxythiolanes are otherwise, i. e., apart from 3-hydroxyl hydrogen, free from hydrogen joined to the thiolane nucleus through 5th and 6th group elements, e. g., N, O, P, As, Se, Te, S, etc.

These new ethers are suitable for many applications ior which it is impossible to use the original polymeric polyhydric alcohols. For example, the 1,1 dioxotetrahydrothienyl-3 ethers of cellulose can be formed, by the application of heat and pressure, into light-colored, translucent sheets and bars which are tough and strong. The organic solvent soluble ethers of polyvinyl alcohol are suitable for the preparation of lacquers and coating compositions. As such, they give tough, water-insoluble films. Solutions of these ethers are also well suited for the preparation of impregnated and coated articles 01' various types, including fabrics, wood, pulp, leather, etc. Unsupported sheeting can be cast from solution, or hot pressed from the ether itself. These films when plasticized are tough and remarkably elastic and rubbery. Articles prepared from polyvinyl 1,1-dioxotetrahydrothienyl-3 ethers of high sulfur content, 1. e., having a small roportion of tree hydroxyls as compared to the number in the original polymer, in contrast to similar items made from polyvinyl alcohol, are insoluble in water.

' As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to, the specific embodiments thereof excep as defined inthe a pended claims.

What is claimed is:

1. An ether or a polymeric p lyhydric alcohol with a 3-hydroxythiolane-1-dioxide, said 3-!!!- droxythiolane-l-dioxide being, apart from the 3-hydroxyl hydrogen, tree from hydrogen joined to the thiolane nucleus through an element selected from the elementsv oi the 5th and 6th groups or the periodic system. I

2. An ether of a 3-hydroxythiolane-L-dioxide with a material having a cellulosic nucleus and free hydroxyls, said 3-hydroxythiolane-1-dioxide being, apart irom the 3-hydr'oxyl hydrogen, tree from. hydrogen Joined to the thiolane nucleus through an element selected from the elements of the 5th and 6th groups of the periodic system.

3. An ether of a '3-hydroxythiolane-1-dioxide with a polyvinyl alcohol, said 3-hydroxythiolanel-dioxide being, apart from the 3-hydroxyl hydrogen, free from hydrogen joined to the thiolane nucleus through an element selected from the elements of the 5th and 6th groups of the periodic system; 7

4. An ether of a 3-hydroxythiolane-1-dioxide with an at least partially hydrolyzed vinyl acetate polymer, said 3-hydroxythiolane-l-dioxide being, apart from the 3 -hydroxyl hydrogen, free from hydrogen Joined to the thiolane nucleus through an element selected from the elements of the 5th and 6th groups or the periodic system.

5. An ether of a polymeric polyhydric alcohol with 3-hydroxythiolane-l-dioxide.

6. An ether of 3-hydroxythiolane-l-dioxide with a material having a cellulosic nucleus and free hydroxyls.

7. An ether of S-hydroXythioIane-I-dioxide with a polyvinyl alcohol.

'having a cellulosic nucleus and tree hydroxyls with a 2,5-dihydrothiophene-l-dioxide inert to sodium at 25 C.

11. Process which comprises heating, at 65-75.

. C. in the presence of aqueous alkali, a polyvinyl alcohol with a 2,5-dihydrothiophene-1-dioxide inert to sodium at 25 C.

12. Process which comprises heating, at 65-75 C. in the presence of aqueous alkali, an at least partially hydrolyzed vinyl acetate polymer with a 2,5-dihydrothiophene-1-dioxide inert to sodium at 25 C. I

13. Process which comprises heating, at 65-75 C. in the presence oi aqueous alkali, an at least partially hydrolyzed vinyl acetate polymer with 2,5-dihydrothiophene-l-dioxide.

14. Process which comprises heating, at 65-75 C. in the presence of aqueous alkali, a polyvinyl alcohol with 2,5-dihydrothiophene-1-dioxide.

WILLIAM AUGUST HOFFMAN. CARL WALTER- MoR'rENsoN.

Patent No. 2,394,776.

' Certificate of Correction WILLIAM AUGUST HOFFMAN ET AL.

"It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, second column, line 38, Example V, for and 2,5 read any 2,5; and that the said Letters Patent should be February 12, 1946.

read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of August, A. D. 1946.

[SEAL] LESLIE FRAZER,

First Assistant Oommisdoner of Patents. 

